Back to EveryPatent.com
United States Patent |
5,074,979
|
Valko
,   et al.
|
December 24, 1991
|
Cationic resin containing blocked isocyanate groups suitable for use in
electrodeposition
Abstract
A cationic resin containing blocked isocyanate groups which is suitable for
use in electrodeposition is disclosed. The cationic resin is derived from
an epoxy resin and contains in the resin molecule cationic salt groups,
active hydrogen groups and blocked isocyanate groups. The blocked
isocyanate groups are incorporated into the resin molecule by reacting the
epoxy resin with a compound selected from the class consisting of mercapto
compounds and acid group-containing compounds where the compounds also
contain blocked isocyanate groups. The resin can be formulated into an
electrocoating composition which is free of lead and yet provides
outstanding corrosion resistance when electrodeposited over steel
substrates. The outstanding corrosion resistance can be attained when the
substrate has not been given a chrome rinse which is conventional in
pretreating the steel substrate before electrodeposition.
Inventors:
|
Valko; Joseph T. (Pittsburgh, PA);
Karabin; Richard F. (Ruffs Dale, PA)
|
Assignee:
|
PPG Industries, Inc. (Pittsburgh, PA)
|
Appl. No.:
|
540991 |
Filed:
|
June 20, 1990 |
Current U.S. Class: |
204/501; 204/505; 523/415; 528/45; 528/73 |
Intern'l Class: |
C25D 013/00 |
Field of Search: |
204/181.7
523/415
528/45,73
|
References Cited
U.S. Patent Documents
3922253 | Nov., 1975 | Jerabek et al. | 260/77.
|
3935087 | Jan., 1976 | Jerabek et al. | 204/181.
|
4007154 | Feb., 1977 | Schimmel et al. | 260/37.
|
4147679 | Apr., 1979 | Scriven et al. | 204/181.
|
4212779 | Jul., 1980 | Schmolzer et al. | 260/22.
|
4260720 | Apr., 1981 | Bosso et al. | 528/109.
|
4452834 | Jun., 1984 | Nachtkamp et al. | 427/379.
|
4468307 | Aug., 1984 | Wismer et al. | 204/181.
|
4480008 | Oct., 1984 | Farronato et al. | 528/45.
|
4536558 | Aug., 1985 | Kordomenos | 528/100.
|
4609446 | Sep., 1986 | Geist et al. | 204/181.
|
4829105 | May., 1989 | Yamada et al. | 528/45.
|
5008351 | Apr., 1991 | Paar | 525/528.
|
Foreign Patent Documents |
317185 | May., 1989 | EP.
| |
Primary Examiner: Niebling; John
Assistant Examiner: Marquis; Steven P.
Attorney, Agent or Firm: Connell; Gary J., Uhl; William J.
Claims
We claim:
1. An electrodepositable composition, comprising a non-gelled cationic
water-dispersible resin electrodepositable on a cathode which is derived
from an epoxy resin and which contains in the resin molecule cationic salt
groups, active hydrogen groups and blocked isocyanate groups, said blocked
isocyanate groups being incorporated into the resin molecule by reacting
said epoxy resin prior to curing said epoxy resin with an acid
group-containing compound, said compound also containing said blocked
isocyanate groups, wherein said acid group-containing compound is prepared
by reacting a partially capped polyisocyanate and a hydroxyl
group-containing acid and wherein said composition is free of lead.
2. The cationic resin of claim 1 in which the epoxy resin is a polyglycidyl
ether of a polyhydric material.
3. The cationic resin of claim 2 in which the polyglycidyl ether of the
polyhydric material is chain extended with a polyhydric phenol.
4. The cationic resin of claim 3 in which the polyhydric phenol is
resorcinol.
5. The cationic resin of claim 1 in which the cationic salt groups are
amine salt groups.
6. The cationic resin of claim 1 in which the amine salt groups are amine
salt groups of sulfamic acid.
7. The cationic resin of claim 1 in which the active hydrogen groups are
selected from the class consisting of primary amine groups, hydroxyl
groups and mixtures thereof.
8. The cationic resin of claim 1 wherein said acid group-containing
compound is a carboxylic acid group-containing compound.
9. The cationic resin of claim 8 wherein said carboxylic acid
group-containing compound is formed from reacting a polyisocyanate, a
hydroxyl group-containing acid and a blocking agent for said
polyisocyanate.
10. The cationic resin of claim 8 wherein said hydroxyl group-containing
acid is dimethylolpropionic acid.
11. The cationic resin of claim 1 in which the polyisocyanate is selected
from the class consisting of diphenylmethane-4,4'-diisocyanate and
mixtures of diphenylmethane-4,4'-diisocyanate and polymethylene
polyphenylisocyanate.
12. The cationic resin of claim 1 in which the isocyanate groups are
blocked with a lower aliphatic alcohol.
13. The cationic resin of claim 12 in which the lower aliphatic alcohol is
selected from the class consisting of methanol, ethanol or mixtures
thereof.
14. An aqueous dispersion containing the cationic resin of claim 1.
15. The aqueous dispersion of claim 14 which is free of lead.
16. A method of electrodepositing an electroconductive substrate which
serves as a cathode in an electrical circuit comprising said cathode and
an anode immersed in an aqueous electrocoating composition containing a
cationic water-dispersible resin, said method comprising passing electric
current between the anode and the cathode to cause the electrocoating
composition to deposit on the cathode as a substantially continuous film,
heating the electrodeposited film at elevated temperature to form a cured
film, characterized in that the cationic water-dispersible resin is
non-gelled, is electrodepositable on a cathode, is derived from an epoxy
resin and contains in the resin molecule cationic salt groups, active
hydrogen groups and blocked isocyanate groups, said blocked isocyanate
groups being incorporated into the resin molecule by reacting said epoxy
resin prior to curing said epoxy resin with a compound selected from the
class consisting of mercapto compounds and acid group-containing
compounds, wherein said acid group-containing compounds are prepared by
reacting a partially capped polyisocyanate and a hydroxyl group-containing
acid, said compounds also containing said blocked isocyanate groups and
the aqueous electrocoating composition is free of lead.
17. The method of claim 16 in which the cathode is steel which has not been
given a chrome rinse pretreatment step.
18. A process for preparing a non-gelled cationic resin comprising:
1) mixing the following ingredients together simultaneously:
i) a polyepoxide,
ii) a polyhydroxyl group-containing material selected from alcoholic
hydroxyl group-containing materials and phenolic hydroxyl group-containing
materials, and
iii) an acid group or mercapto group-containing material which also
contains a blocked isocyanate group;
2) heating the mixture to form a resinous reaction product wherein the
mercapto groups or acid groups of said compound are reacted with epoxy
groups of said epoxy resin;
3) reacting said resinous reaction product with a cationic salt group
former to form said cationic resin.
19. The process of claim 18 in which said polyepoxide is a polyglycidyl
ether of a polyphenol.
20. The process of claim 18 in which said resinous reaction product is
epoxy group-containing resin.
21. The process of claim 20 in which the resinous reaction product has an
epoxy equivalent based on solids of 1200 to 2500.
22. The process of claim 18 in which the polyhydroxyl group-containing
material is selected from the class consisting of polyether polyols,
resorcinol and mixtures thereof.
23. The process of claim 22 in which the polyether polyol is formed from
reacting
(A) a cyclic polyol with
(B) ethylene oxide or a mixture of ethylene oxide and an alkylene oxide
having 3 to 8 carbon atoms in the alkylene chain;
the equivalent ratio of (B) to (A) being within the range of 3 to 20:1.
24. The process of claim 18 in which the acid group-containing compound
(iii) is formed from reacting a polyisocyanate, a hydroxyl
group-containing acid and a blocking agent for said polyisocyanate.
25. The process of claim 24 in which the hydroxyl group-containing acid is
dimethylolpropionic acid.
26. The process of claim 24 in which the polyisocyanate is selected from
the class consisting of diphenylmethane-4,4'-diisocyanate and mixtures of
diphenylmethane-4,4'-diisocyanate and polymethylene polyphenylisocyanate.
27. The process of claim 24 in which the blocking agent is a lower
aliphatic alcohol.
28. The process of claim 27 in which the lower aliphatic alcohol is
selected from the class consisting of methanol, ethanol and mixtures
thereof.
29. The process of claim 18 in which the cationic salt group formers are
mixtures of acids and members of the class consisting of primary amines,
secondary amines, tertiary amines and sulfide groups including mixtures
thereof.
30. A non-gelled cationic water-dispersible resin electrodepositable on a
cathode which is derived from an epoxy resin and which contains in the
resin molecule cationic salt groups, active hydrogen groups and blocked
isocyanate groups, said blocked isocyanate groups being incorporated into
the resin molecule by reacting said epoxy resin prior to curing said epoxy
resin with a mercapto compound, said compound also containing said blocked
isocyanate groups.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to cationic resins and to their use in
electrodeposition, and more particularly, relates to cationic resins
containing blocked isocyanate groups and to their use in electrodeposition
over steel substrates.
2. Brief Description of the Prior Art
Electrodeposition as a coating application method involves deposition of a
film-forming composition under the influence of an applied electrical
potential. Electrodeposition has become increasingly important in the
coatings industry because by comparison with non-electrophoretic coating
means, electrodeposition offers higher paint utilization, outstanding
corrosion protection and low environmental contamination. Initially,
electrodeposition was conducted with the workpiece being coated serving as
the anode. This was familiarly referred to as anionic electrodeposition.
However, in 1972, cationic electrodeposition was introduced commercially.
Since that time, cationic electrodeposition has steadily gained in
popularity and today is by far the most prevalent method of
electrodeposition. Throughout the world, more than 80 percent of all motor
vehicles produced are given a primer coating by cationic
electrodeposition.
To achieve the best corrosion resistance over steel substrates, the
cationic electrodepositable composition is formulated with lead either as
a pigment or as a soluble lead salt. However, lead is a very toxic
material and as such presents many difficulties to the paint supplier and
paint customer. The lead often finds its way into the effluent of the
electrodeposition process which necessitates costly treatment processes to
remove the lead. Also, to achieve optimum corrosion resistance, the steel
substrate is usually pretreated prior to electrodeposition with a
phosphate conversion coating and given a chromic acid rinse (chrome rinse)
at the conclusion of the pretreatment process. Chromium is also a toxic
material and effluent from the pretreatment process containing chromium
must be treated and disposed of in a safe and ecological manner. This
treatment process can be very costly.
SUMMARY OF THE INVENTION
In accordance with the present invention, a cationic resin, its method of
preparation and the use of the resin in the process of cationic
electrodeposition is provided. Electrodepositable aqueous dispersions of
the cationic resin when electrocoated over steel substrates provide
outstanding corrosion resistance even when the dispersions are free of
lead and the steel substrate has not been pretreated and given a chrome
rinse. The cationic resin is derived from an epoxy resin and contains in
the resin molecule cationic salt groups, active hydrogen groups and
blocked isocyanate groups. The blocked isocyanate groups are incorporated
into the resin molecule by reacting the epoxy resin with a compound
selected from the class consisting of mercapto compounds and acid
group-containing compounds in which the compounds also contain blocked
isocyanate groups. The acid group-containing compounds are preferred.
DETAILED DESCRIPTION
The cationic water-dispersible resin of the present invention can be
prepared by mixing together a polyepoxide, a polyhydroxyl group-containing
material selected from alcoholic hydroxyl group-containing materials and
phenolic hydroxyl group-containing materials and an acid or mercapto
group-containing material which also contains blocked isocyanate groups.
The mixture is heated to form a resinous reaction product which is further
reacted with a cationic salt group former to form the cationic resin.
The invention also provides for a method of cationic electrodeposition
using aqueous dispersions of the cationic resin.
The polyhydroxyl group-containing material and the acid or the mercapto
group-containing compound which contains a blocked isocyanate group
compete with one another for reaction with the epoxy functionality in the
polyepoxide. The reaction can be conducted neat or in the presence of an
organic solvent such as ketones such as methyl isobutyl ketone and methyl
amyl ketone, aromatics such as toluene and xylene and glycol ethers such
as the dimethylether of diethylene glycol. Typically, reaction is
conducted at a temperature of from 95.degree. to 105.degree. C. for about
60 to 180 minutes until an epoxy group-containing resinous reaction
product is obtained. Typically, the reaction product will have an epoxy
equivalent based on solids of no greater than 3000, preferably from about
1200 to 2500.
The equivalent ratio of reactants, i.e., epoxy:polyhydroxyl
group-containing material:acid or mercapto compound containing blocked
isocyanate groups typically is from 1:0.10 to 0.75:0.25 to 0.60.
Examples of polyepoxides are those having a 1,2-epoxy equivalency greater
than one and preferably about two, that is, polyepoxides which have on an
average basis two epoxy groups per molecule. The preferred polyepoxides
are polyglycidyl ethers of cyclic polyols. Particularly preferred are
polyglycidyl ethers of polyhydric phenols such as bisphenol A. These
polyepoxides can be produced by etherification of polyhydric phenols with
epihalohydrin or dihalohydrin such as epichlorohydrin or dichlorohydrin in
the presence of alkali. Besides polyhydric phenols, other cyclic polyols
can be used in preparing the polyglycidyl ethers of cyclic polyol
derivatives. Examples of other cyclic polyols would be alicyclic polyols,
particularly cycloaliphatic polyols such as 1,2-cyclohexanediol and
1,2-bis(hydroxymethyl)cyclohexane. The preferred polyepoxides have
molecular weights of at least 200 and preferably within the range of 200
to 2000, and more preferably about 340 to 2000. Epoxy group-containing
acrylic polymers can also be used, but their use is not preferred.
Examples of polyhydroxyl group-containing materials to chain extend or
advance the molecular weight of the epoxy resin (i.e., through
hydroxyl-epoxy reaction) can be selected from alcoholic hydroxyl
group-containing materials and phenolic hydroxyl group-containing
materials. Examples of alcoholic hydroxyl group-containing materials are
simple polyols such as neopentyl glycol as described in Canadian Patent
1,179,443; polyester polyols such as described in U.S. Pat. No. 4,148,772;
polyether polyols such as described in U.S. Pat. No. 4,468,307 and
urethane diols such as described in U.S. application Ser. No. 07/315,954.
Examples of phenolic hydroxyl group-containing materials are polyhydric
phenols such as bisphenol A, phloroglucinol and resorcinol. Mixtures of
alcoholic and phenolic hydroxyl group-containing materials can be used. A
preferred polyhydroxyl group-containing material is a polyether polyol of
the type disclosed in U.S. Pat. No. 4,419,467. These polyether polyols are
formed from reacting (A) cyclic polyols such as polyhydric phenols such as
bisphenol A or resorcinol and cycloaliphatic polyols such as
1,2-cyclohexanediol or 1,4-cyclohexanedimethanol with (B) ethylene oxide
or a mixture of ethylene oxide and an alkylene oxide having 3 to 8 carbon
atoms in the alkylene group, i.e., propylene oxide, the molar ratio of (B)
to (A) being within the range of 3 to 20:1. Preferably, the polyether
polyol is used in admixture with a polyhydric phenol such as resorcinol.
As mentioned above, the polyhydroxyl group-containing material is
preferably reacted with a polyepoxide simultaneously with the acid or the
mercapto functional material containing the blocked isocyanate groups.
Alternately, the polyepoxide can be first reacted with the polyhydroxyl
group-containing material to chain extend or advance the epoxy resin
followed by reaction with the acid or mercapto functional material
containing the blocked isocyanate groups.
The acid group or mercapto group-containing compound which also contains
the blocked isocyanate groups can be prepared by reacting a hydroxyl
group-containing acid material or a hydroxyl group-containing mercapto
material with a partially capped polyisocyanate. Preferably, the acid or
mercapto-functional compound is monofunctional with regard to the acid or
mercapto groups. The isocyanate functionality will react preferentially
with the hydroxyl groups leaving the acid or mercapto groups available for
subsequent reaction with the epoxy functionality. Reaction is usually
conducted in the presence of an inert organic solvent such as ketones such
as acetone, methyl ethyl ketone and methyl isobutyl ketone, and glycol
ethers such as the dimethylether of diethylene glycol and a catalyst, for
example, a tin catalyst such as dibutyltin dilaurate. Reaction is usually
conducted until the resultant reaction product is substantially free of
isocyanate functionality. Typical reaction temperatures and times are from
40.degree. to 100.degree. C. for about 30 to 400 minutes. Examples of
suitable hydroxyl-containing acids are hydroxyl group-containing
carboxylic acids such as dimethylolpropionic acid, malic acid and
12-hydroxystearic acid. Examples of hydroxyl group-containing mercapto
compounds are 1-thioglycerol, mercaptoethanol and mercaptophenol.
Examples of suitable polyisocyanates are aromatic and aliphatic, including
cycloaliphatic polyisocyanates. Representative examples include 2,4- or
2,6-toluene diisocyanate including mixtures thereof and p-phenylene
diisocyanate, tetramethylene and hexamethylene diisocyanate and
dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate,
diphenylmethane-4,4'-diisocyanate and polymethylene polyphenyl isocyanate.
Higher polyisocyanates such as triisocyanates can be used and an example
would include triphenylmethane-4,4',4"-triisocyanate. NCO-prepolymers such
as reaction products of polyisocyanates with polyols such as neopentyl
glycol and trimethylolpropane and with polymeric polyols such as
polycaprolactone diols and triols (NCO/OH equivalent ratio greater than
one) can also be used. A mixture containing
diphenylmethane-4,4'-diisocyanate and polymethylene polyphenyl isocyanate
is preferred because it provides better flow and reduces crystallinity
with the preferred low molecular weight blocking agents methanol and
ethanol described below.
Any suitable aliphatic, cycloaliphatic, aromatic alkyl monoalcohol and
phenolic compound may be used as a capping agent in accordance with the
present invention such as, for example, lower aliphatic alcohols
containing from 1 to 4 carbon atoms such as methanol, ethanol and n-butyl
alcohol; cycloaliphatic alcohols such as cyclohexanol; aromatic-alkyl
alcohols such as phenyl carbinol and methylphenyl carbinol; phenolic
compounds such as phenol itself, substituted phenols in which the
substituents do not adversely affect coating operations. Examples include
cresol and nitrophenol.
Additional capping agents include oximes such as methyl ethyl ketoxime,
acetone oxime and cyclohexanone oxime and lactams such as
epsilon-caprolactam. Preferred blocking agents are methanol and ethanol
because these materials, although they volatilize from film on cure, do
not contribute significantly to weight loss in the film.
Usually, sufficient polyisocyanate is present in the cationic polymer such
that there is about 0.1 to about 1.2 capped isocyanate groups for each
active hydrogen, i.e., hydroxyl, primary and secondary amino.
Usually the polyisocyanate is partially capped before reaction with the
hydroxyl group-containing acid or hydroxyl group-containing mercaptan to
partially defunctionalize the polyisocyanate and to minimize the danger of
gelation.
The resinous reaction product prepared as described above is then further
reacted with a cationic salt group former. By cationic salt group former
is meant a material which is reactive with epoxy groups and which can be
acidified after, during or before reaction with the epoxy groups to form
cationic salt groups. Examples of such materials are amines such as
primary or secondary amines which can be acidified after reaction with the
epoxy groups to form amine salt groups, or tertiary amines which can be
acidified prior to reaction with the epoxy groups and which after reaction
with the epoxy groups form quaternary ammonium salt groups. Examples of
other cationic salt group formers are sulfides which can be mixed with
acid prior to reaction with the epoxy groups and form ternary sulfonium
salt groups upon subsequent reaction with the epoxy groups.
With regard to the amines, the preferred amines are monoamines,
particularly hydroxyl-containing amines. Polyamines such as
ethylenediamine and diethylenetriamine and triethylenetetraamine can be
used but their use is not preferred because they are multifunctional and
have a tendency to gel the reaction mixture. If polyamines are used, they
should be used in a substantial stoichiometric excess with the epoxy
functionality in the resinous reaction product (epoxy resin) so as to
avoid the danger of gelation and the excess polyamine removed from the
reaction mixture such as by vacuum stripping.
Tertiary and secondary amines are preferred to primary amines because the
primary amines are polyfunctional with regard to reaction with epoxy
groups and have a greater tendency to gel the reaction mixture. When using
polyamines or primary amines, special precautions should be taken to
minimize the danger of gelation, for example, excess amine can be used and
the excess vacuum stripped at the completion of the reaction. Also, the
epoxy resin can be added to the amine to insure that excess amine will be
present. Examples of hydroxyl-containing amines are alkanolamines,
dialkanolamines, trialkanolamines, alkylalkanolamines and
arylalkylalkanolamines containing from 1 to 18, preferably 1 to 6 carbon
atoms each in the alkanol, alkyl and aryl chains. Specific examples
include ethanolamine, N-methylethanolamine, diethanolamine,
N-phenylethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine,
triethanolamine and N-(2-hydroxyethyl)-piperazine.
Amines which do not contain hydroxyl groups such as mono, di and
trialkylamines and mixed alkyl-aryl amines and substituted amines in which
the substituents are other than hydroxyl and in which the substituents do
not detrimentally affect the epoxy-amine reaction product can also be
used. Specific examples of these amines are ethylamine, methylethylamine,
triethylamine, N-benzyldimethylamine, dicocoamine and
N,N-dimethylcyclohexylamine.
Mixtures of the various amines described above can be used.
The reaction of the primary and/or secondary amine with the epoxy resin
takes place upon mixing the amine with the epoxy resin. Reaction can be
conducted neat or optionally in the presence of a suitable solvent.
Reaction may be exothermic and cooling may be desired. However, heating to
a moderate temperature, that is, within the range of 50.degree. to
150.degree. C., may be used to hasten the reaction.
The reaction product of the primary or secondary amine with the epoxy resin
attains its cationic character by at least partial neutralization with
acid. Examples of suitable acids include organic and inorganic acids such
as formic acid, acetic acid, lactic acid, sulfamic acid, which is
preferred, and phosphoric acid. The extent of neutralization will depend
upon the particular product involved. It is only necessary that sufficient
acid be used to disperse the product in water. Typically, the amount of
acid used will be sufficient to provide at least 20 percent of all of the
total theoretical neutralization. Excess acid beyond that required for 100
percent total theoretical neutralization can also be used.
In the reaction of the tertiary amine with the epoxy resin, the tertiary
amine can be prereacted with the acid such as those mentioned above to
form the amine salt and the salt reacted with the epoxy resin to form the
quaternary ammonium salt group-containing resin. The reaction is conducted
by mixing the amine salt and the epoxy resin together in the presence of
water. Typically, the water is employed on the basis of about 1.75 to
about 20 percent by weight based on total reaction mixture solids.
In forming the quaternary ammonium salt group-containing resin, the
reaction temperature can be varied between the lowest temperature at which
reaction reasonably proceeds, for example, room temperature, or in the
usual case, slightly above room temperature to a maximum temperature of
100.degree. C. (at atmospheric pressure). At greater than atmospheric
pressure, higher reaction temperatures can be used. Preferably, the
reaction temperature range is between about 60.degree. to 100.degree. C.
Solvent for the reaction is usually not necessary, although solvents such
as a sterically hindered ester, ether or sterically hindered ketone may be
used if desired.
In addition to the primary, secondary and tertiary amines disclosed above,
a portion of the amine which is reacted with the epoxy resin can be a
ketimine of a polyamine. This is described in U.S. Pat. No. 4,104,147 at
column 6, line 23 to column 7, line 23, the portions of which are hereby
incorporated by reference. The ketimine groups will decompose upon
dispersing the amine-epoxy resin reaction product in water resulting in
free primary amine groups which would be reactive with the isocyanate
curing agents.
Besides resins containing amine salts and quaternary ammonium salt groups,
resins containing ternary sulfonium cationic groups can be used in the
practice of the invention. Examples of these cationic resins and their
method of preparation are described in U.S. Pat. Nos. 3,793,278 to DeBona
and 3,959,106 to Bosso and Wismer.
The extent of cationic salt group formation of the resin should be selected
that when the resin is mixed with aqueous medium, a stable dispersion will
form. A stable dispersion is one which does not settle or is one which is
easily redispersible if some sedimentation occurs. In addition, the
dispersion should be of sufficient cationic character that the dispersed
resin particles will migrate towards and electrodeposit on the cathode
when an electrical potential is impressed between an anode and a cathode
immersed in the aqueous dispersion.
In general, most of the cationic resins prepared by the process of the
invention contain from about 0.1 to 3.0, preferably from about 0.1 to 0.7
milliequivalents of cationic group per gram of resin solids. Obviously,
one must use the skill of the art to couple the molecular weight and the
cationic group content to arrive at a satisfactory product. Accordingly,
the resinous reaction products of the present invention preferably have
number average molecular weights of about 5,000 to 15,000 and more
preferably from about 6,000 to 10,000.
The active hydrogens associated with the cationic resins of the invention
can be selected from any of the active hydrogens which are reacted with
isocyanates over the temperature range of 93.degree.-204.degree. C.,
preferably 121.degree.-177.degree. C. Typically, the active hydrogens will
be associated with hydroxyl, primary and secondary amino including mixed
groups such as hydroxyl and primary amino. Preferably, the cationic
resinous reaction products of the present invention will have an active
hydrogen content of at least 2 to 10 and preferably from about 2.5 to 5
milliequivalents of active hydrogen per gram of resin solids.
The resins of the present invention are non-gelled and are used in the
electrodeposition process in the form of aqueous dispersions. The term
"dispersion" as used within the context of the present invention is
believed to be a two-phase transparent, translucent or opaque aqueous
resinous system in which the resin is the dispersed phase and water the
continuous phase. Average particle size diameter of the resinous phase is
usually less than 10 and preferably less than 5 microns. The concentration
of the resinous phase in the aqueous medium depends upon the particular
end use of the dispersion and in general is not critical. For example, the
aqueous dispersion preferably contains at least about 0.05 and usually
from about 0.05 to 50 percent by weight resin solids. By "non-gelled" is
meant the cationic resins are substantially free of crosslinking and the
resinous reaction products (prior to cationic salt group formation) have
an intrinsic viscosity when dissolved in a suitable solvent. Intrinsic
viscosity of the reaction product is an indication of its molecular
weight. A gelled reaction product on the other hand since it has an
essentially infinitely high molecular weight will have an intrinsic
viscosity too high to measure.
Besides water, the aqueous medium may contain a coalescing solvent. Useful
coalescing solvents include hydrocarbons, alcohols, esters, ethers and
ketones. The preferred coalescing solvents include alcohols, polyols,
ethers and ketones. Specific coalescing solvents include isopropanol,
butanol, 2-ethylhexanol, isophorone, 4-methoxy-2-pentanone, ethylene and
propylene glycol and the monoethyl, monobutyl and monohexyl ethers of
ethylene glycol. The amount of the coalescing solvent is not unduly
critical and is generally present in an amount of up to 40 percent by
weight, preferably, about 0.05 to about 25 percent by weight based on
total weight of the aqueous medium.
When formulated into a coating composition for use in cationic
electrodeposition, the aqueous resinous dispersion described above is
usually combined with pigments and various additives such as plasticizers,
surfactants, wetting agents, defoamers and anti-cratering agents.
The pigment composition may be any of the conventional types comprising,
for example, iron oxides, carbon black, coal dust, titanium dioxide, talc
and barium sulfate. One of the advantages of using aqueous dispersions of
the present invention in the process of cationic electrodeposition is the
outstanding corrosion resistance they provide to steel substrates without
the need for a lead-containing pigment. However, lead pigments may be
used, if desired. The pigment content of the dispersion is usually
expressed as the pigment to resin ratio. In the practice of the invention,
the pigment to resin ratio is usually within the range of 0.1 to 1:1.
Examples of surfactants and wetting agents include alkyl imidazolines such
as those available from Geigy Industrial Chemicals as GEIGY AMINE C,
acetylenic alcohols available from Air Products and Chemicals as SURFYNOL.
Examples of defoamers are FOAM KILL 63, hydrocarbon oil containing inert
diatomaceous earth. Examples of anti-cratering agents are
polyoxyalkylene-polyamine reaction products such as those described in
U.S. Pat. No. 4,432,850. These optional ingredients when present
constitute up to 30, usually 1 to 20 percent by weight of resin solids.
Curing catalysts such as tin catalysts are usually present in the
composition. Examples are dibutyltin dilaurate and dibutyltin oxide. When
used, they are typically used in amounts of 0.05 to 5 percent by weight
based on weight of resin solids.
In the process of electrodeposition the aqueous dispersion is placed in
contact with an electrically conductive anode and an electrically
conductive cathode. Upon passage of the electric current between the anode
and cathode while in contact with the aqueous dispersion, an adherent film
of the coating composition will deposit in a substantially continuous
manner on the cathode. The conditions under which electrodeposition is
carried out are well known in the art. Electrodeposition is usually
carried out at a constant voltage. The applied voltage may vary greatly
and can be, for example, as low as 1 volt or as high as several thousand
volts, although typically between 50 volts and 500 volts are employed.
Current density is usually between about 1.0 ampere and 15 amperes per
square foot (10.8-161.5 amperes per square meter) and tends to decrease
quickly during electrodeposition indicating formation of a continuous
self-insulating film. Any electroconductive substrate especially metal
such as steel, zinc, aluminum, copper, magnesium or the like can be
electrodeposited with the coating compositions of the present invention.
However, the invention is particularly desirable for the coating of steel
substrates because of the outstanding corrosion resistance it provides to
the substrate. Although it is conventional to pretreat the steel substrate
with a phosphate conversion coating followed by a chromic acid rinse
before electrodeposition, the electrodeposition process of the present
invention can be utilized with steel substrates which have not been given
a chrome rinse and still provide for outstanding corrosion resistance.
After deposition, the coating is cured at elevated temperatures by any
convenient method such as by baking in ovens. The curing temperature will
typically be conducted over the range of from about 120.degree. to
250.degree. C., preferably from 120.degree. to 190.degree. C., for
anywhere from 10 to 60 minutes. The thickness of the resultant film will
typically vary from about 10 to 50 microns.
The aqueous resinous dispersions of the present invention besides being
applied by electrodeposition could also be applied by conventional coating
applications such as flow, dip, spray and roll coating applications.
Illustrating the invention are the following examples which, however, are
not to be construed as limiting the invention to their details. All parts
and percentages in the examples as well as throughout the specification
are by weight unless otherwise indicated.
EXAMPLES
Vehicle Resins
EXAMPLE A
The following Example shows the preparation of an acid-functional compound
which also contains blocked isocyanate groups and mixing the resultant
acid-functional compound with a bisphenol A-ethylene oxide adduct for
subsequent reaction with a polyepoxide in Example 1.
Into a 12-liter flask which was equipped with a stirrer, a condenser, a
nitrogen inlet, a thermometer and an addition funnel was placed 2820.0
grams (21.54 equivalents) of a mixture of diphenyl-4,4'-diisocyanate and
polyphenyl polyisocyanate available from Mobay Chemical Co. as MONDUR
MRS-4, 640.1 grams of methyl isobutyl ketone and 0.52 gram of dibutyltin
dilaurate. A nitrogen blanket was begun. Into the addition funnel was
charged a total of 508.0 grams of a blend consisting of 56.8 to 58.8
percent methanol with 40.7 to 42.7 percent ethanol and 0.35 to 0.65
percent methyl isobutyl ketone. While stirring the polyisocyanate
solution, the alcohol blend was added dropwise, beginning at ambient
temperature, over a period of about 1.5 hours, while keeping the
temperature primarily in the 60.degree.-65.degree. C. range. After the
addition was complete, a temperature of 65.degree. C. was maintained for 1
hour, at which time the NCO equivalent was determined to be 512. At that
point, 3.41 grams of dibutyltin dilaurate and 505.4 grams (7.54
equivalents of hydroxyl) of dimethylolpropionic acid were added. The
reaction mixture was heated to 95.degree. C. and held there until only a
very weak isocyanate absorbance was detected by infrared spectroscopy. At
that point, 1375.6 grams (5.77 equivalents) of a bisphenol A-ethylene
oxide polyol (mole ratio 1:7) and a total of 1093.2 grams of methyl
isobutyl ketone were added and mixed to homogeneity. The product had a
75.3 percent solids content (1 hour at 110.degree. C.), an acid value of
30.76 (theoretical 30.47) and 0.11 percent water.
EXAMPLE B
The following Example shows the preparation of a mercapto-functional
compound which also contains blocked isocyanate groups and mixing the
resultant mercapto-functional compound with a bisphenol A-ethylene oxide
adduct for subsequent reaction with a polyepoxide in Example 3.
A 5-liter flask equipped with a stirrer, a condenser, a nitrogen inlet, a
thermometer and an addition funnel was charged with 1229.5 grams (9.55
equivalents) of MONDUR MRS-4 (a product of Mobay Corporation), 279.1 grams
of methyl isobutyl ketone (MIBK) and 0.23 grams of dibutyltin dilaurate. A
nitrogen blanket was established. The addition funnel was charged with
230.0 grams of a blend consisting of 56.8 to 58.8 percent by weight
methanol with 40.7 to 42.7 percent ethanol and 0.35 to 0.65 percent MIBK.
The alcohol blend was added dropwise to the stirred polyisocyanate
solution beginning at ambient temperature up to a temperature of
55.degree.-65.degree. C. over a period of about 2 hours. After completion
of the addition, the reaction mixture was held at 60.degree. C. for one
hour. At that point, the NCO equivalent was determined to be 546. To this
was added 1.5 grams of dibutyltin dilaurate and 171.2 grams (3.17
equivalents of hydroxyl) of 3-mercapto-1,2-propanediol. The temperature
was raised to 95.degree. C. and held there until only a very weak
isocyanate absorbance was detected by infrared spectroscopy. At that
point, 424.3 grams of MIBK was added and the mixture stirred to
homogeneity. The product had a 71.6 percent solids content with a
mercaptan equivalent of 0.634 (theoretical 0.695).
EXAMPLE C
The following Example shows the preparation of a fully blocked
isocyanate-containing compound with no acid or mercapto functionality
(neopentyl glycol-MONDUR MRS-4-adduct blocked with methanol-ethanol) for
the purpose of comparison with those of Examples A and B. The crosslinker
was combined with a bisphenol A-ethylene oxide adduct for subsequent
reaction with a polyepoxide in Comparative Example 5.
Into a 12-liter flask which was equipped with a stirrer, a condenser, a
nitrogen inlet, a thermometer and an addition funnel was placed 2338.2
grams (17.99 equivalents) of MONDUR MRS-4, 530.8 grams of MIBK and 0.4
grams of dibutyltin dilaurate. A nitrogen blanket was established. Into
the addition funnel was charged 411.6 grams of a blend consisting of 56.8
to 58.8 percent methanol with 40.7 to 42.7 percent ethanol and 0.35 to
0.65 percent MIBK. While stirring the polyisocyanate solution, the alcohol
blend was added dropwise, beginning at ambient temperature, up to
60.degree.-65.degree. C. over a period of about 2.5 hours. After the
addition was complete, a temperature of about 65.degree. C. was maintained
for one hour, at which time the NCO equivalent was determined to be 524.
To this was added 163.6 grams (3.15 equivalents) of neopentyl glycol
followed by heating to 74.degree. C. About 30 minutes after the first
addition, the second 163.6 grams of the glycol was added and the reaction
mixture was heated to 95.degree. C. and held there until the 4.4 micron
peak in the infrared spectrum became negligible (this required the
addition of 10.0 grams of the glycol). A solution of 114.0 grams of 1:7
bisphenol A:ethylene oxide diol in 214.0 grams of MIBK was heated to
reflux under a water trap and nitrogen to ensure its dryness and then
added to this blocked isocyanate and the whole was blended to yield a
homogeneous resin solution at 87.5 percent solids.
EXAMPLE D
The following Example shows the preparation of a partially blocked
isocyanate-containing compound (MONDUR MRS methanol-ethanol NCO:OH
equivalent ratio of 1.2:1) for the purpose of comparison with those of
Examples A and B. The crosslinker was combined with a bisphenol A-ethylene
oxide adduct for subsequent reaction with a polyepoxide in Comparative
Example 6.
A 5-liter flask equipped with a stirrer, a condenser, a nitrogen inlet, a
thermometer and an addition funnel was charged with 1790.0 grams (13.90
equivalents) of MONDUR MRS-4, 406.3 grams of methyl isobutyl ketone and
0.33 gram of dibutyltin dilaurate. A nitrogen blanket was begun. A total
of 401.3 grams of a blend consisting of 56.8 to 58.8 percent methanol and
40.7 to 42.7 percent ethanol and 0.35 to 0.65 percent methyl isobutyl
ketone was added dropwise to the stirred polyisocyanate solution over a
period of about 2.25 hours, beginning at ambient temperature and rising to
predominantly 60.degree.-65.degree. C. After the addition was completed,
the reaction mixture was held at 65.degree. C. for one hour, whereupon the
NCO equivalent was determined to be 1021 at 77.6 percent solids.
EXAMPLE 1
This Example shows the preparation of a cationic, water dispersible resin
in accordance with the present invention using the acid-functional
compound containing blocked isocyanate groups of Example A.
A 12-liter flask equipped with a stirrer, a condenser, a nitrogen inlet,
and a thermometer was charged with 4334.4 grams (862.3 grams polyol,
2397.2 grams acid-functional material, 2.4 equivalents acid) of the
mixture of Example A, 2537.5 grams (13.56 equivalents) of bisphenol A
diglycidyl ether, and 488.9 grams (8.89 equivalents) of resorcinol. Under
a nitrogen blanket, these ingredients were stirred while being heated to
90.degree. C. At 90.degree. C., 4.3 grams of benzyl dimethylamine were
added and the temperature was raised to 105.degree. C. The reaction
mixture was held at 105.degree. C. for one hour. An additional 5.6 grams
of benzyl dimethylamine were then added and the reaction was held at
105.degree. C. until an epoxy equivalent (solids) of 1639 gram/equivalent
was reached, evidencing a Gardner-Holdt viscosity of W- at 60 percent
solids in 1-methoxy-2-propanol. At that point was added 129.8 grams (1.02
equivalents of amine) of the diethylene triamine diketimine of methyl
isobutyl ketone at about 70 percent in excess ketone, 87.7 grams (1.35
equivalents of amine) of N-(2-hydroxyethyl)-piperazine, 170.5 grams (0.45
equivalent) of dicocoamine, 131.2 grams (1.75 equivalents) of
N-methylethanolamine and 31.0 grams (0.21 equivalent) of
2-tert-butylphenol. The temperature was adjusted to 113.degree. C. and
held for one hour. At that point, solvent was removed under reduced
pressure to raise the theoretical solids content to 89 percent.
Of this resin, 7200 grams (6408 grams solids) was added to a mixture of
2410.6 grams of deionized water, 147.0 grams (1.52 equivalents) of
sulfamic acid and 100.9 grams of a surfactant blend while stirring. The
surfactant blend was prepared by blending 120 grams of alkyl imidazoline
commercially available from Geigy Industrial Chemicals as GEIGY AMINE C,
120 parts by weight of an acetylenic alcohol commercially available from
Air Products and Chemicals, Inc. as SURFYNOL 104, 120 parts by weight of
2-butoxyethanol and 211 parts by weight of deionized water and 19 parts by
weight of glacial acetic acid.
After one hour stirring, deionized water totalling 8030.9 grams was added
gradually with continued stirring.
This dispersion was diluted with a total of 1834.0 grams of deionized
water, warmed to 60.degree.-66.degree. C. and exposed to reduced pressure
to remove volatile organic solvents to yield a dispersion of 37.6 percent
solids with a particle size of 2220 Angstroms.
EXAMPLE 2
The following Example shows the formulation of a lead-free cationic
electrodeposition paint using the aqueous cationic resinous dispersion of
Example 1. Bimetallic (untreated steel-untreated hot dipped galvanized
steel) coach joints and untreated steel panels were electrocoated in the
paint, cured and evaluated generally in accordance with General Motors
Scab Corrosion testing method TM54-26.
For the purpose of comparison, identical substrates were electrocoated and
cured with UNI-PRIME cationic electrodeposition paint available from PPG
Industries, Inc. and compared with the substrate coated in accordance with
the invention. The UNI-PRIME paint, specifically ED-3150, contained lead.
To 1182.4 grams of the dispersion of Example 1 was added 86.1 grams of a
34.4 percent solids stripped dispersion of an adduct prepared from
JEFFAMINE D2000 and EPON 828 and containing 15 percent crosslinker
prepared generally in accordance with Example H of U.S. Pat. No. 4,419,467
with the exception that the neutralizing acid was sulfamic instead of
acetic (35 percent total theoretical neutralization).
A paint was formed by adding to the dispersion 22.6 grams of the formal of
2-(2-n-butoxyethoxy) ethanol, 14.6 grams of 2-hexoxyethanol, 279.4 grams
of a pigment paste which contributed 11.6 grams of dibutyltin oxide, 3.4
grams of carbon black and 124.4 grams of titanium dioxide (but no lead).
The paint was thinned with 1416.2 grams of deionized water to yield a
paint having a pH of 5.60 and 1432 micromhos conductivity. The paint was
ultrafiltered 20 percent of the total paint weight and replenished with
deionized water, reducing the conductivity to 1219 and the pH to 5.43.
Untreated (no phosphate pretreatment; no chrome rinse) steel coach joints
and panels were electrocoated at 215 volts for 2 minutes with the paint at
85.degree. F. After rinsing with deionized water and air drying, the coach
joints and panels were baked for 30 minutes at 340.degree. F. and
subjected to GM Scab Corrosion cyclic testing and compared to similar
substrates coated with UNI-PRIME electrocoat paint (ED 3150), which
contains lead.
After twenty (20) cycles, the test paint rated a 6 over bimetallic coach
joints on a scale of 1 to 10 with 10 being best, while ED 3150 rated 7.
Over untreated steel flat panels, the test paint rated 2 versus 4 for ED
3150 after 20 cycles. Performances over phosphated steel substrates given
a chrome rinse were equal after 20 cycles.
EXAMPLE 3
This Example shows the preparation of a cationic, water-dispersible resin
in accordance with the present invention using the mercapto-functional
compound containing blocked isocyanate groups of Example B.
A 5-liter flask equipped with a stirrer, a condenser, a nitrogen inlet and
a thermometer was charged with 936.4 grams (670.5 grams solids, 0.59
equivalents mercaptan) of the mercaptan-functional crosslinker of Example
B, 273.0 grams (244.9 grams solids, 1.00 equivalents) of
azeotropically-dried bisphenol A:ethylene oxide diol (1:7 mole ratio) in
methyl isobutyl ketone, 720.6 grams (3.85 equivalents) of bisphenol A
diglycidyl ether and 138.9 grams (2.53 equivalents) of resorcinol. Under a
nitrogen blanket, the mixture was heated to 90.degree. C. At 90.degree.
C., 1.8 grams of benzyl dimethylamine was added and the mixture was heated
to 105.degree. C., where it was held until an epoxy equivalent of 1636 was
reached, evidencing a Gardner-Holdt viscosity of S at 60 percent solids in
1-methoxy-2-propanol. At that point, 36.5 grams (0.1 mole, 0.29
equivalents) of the MIBK diketimine of diethylene triamine in excess MIBK,
25.1 grams (0.19 mole) of N-(2-hydroxyethyl)-piperazine, 48.8 grams of
dicocoamine, 37.5 grams (0.50 equivalents) of N-methylethanolamine and 8.8
grams (0.06 equivalents) of o-t-butylphenol were added. The temperature
was adjusted to 115.degree. C. and held there for one hour. At that point,
solvent was removed under reduced pressure to raise the theoretical solids
content to 89 percent.
Of this resin, 1775 grams was poured into a mixture of 594.5 grams of
deionized water containing 36.4 grams (0.38 equivalents) of sulfamic acid
and 24.9 grams of the surfactant blend used in Example 1. After one hour,
a total of 1980.5 grams of deionized water was added gradually with
stirring.
This dispersion was diluted with a total of 744.0 grams of deionized water,
warmed to 60.degree.-65.degree. C. and exposed to reduced pressure to
remove volatile organic solvents. The stripped dispersion had a solids
content of 38.7 percent and a particle size of 1960 Angstroms.
EXAMPLE 4
The following Example shows the formulation of a lead-free cationic
electrodeposition paint using the aqueous cationic resinous dispersion of
Example 3. Zinc-phosphate-chromic acid rinse pretreated steel panels and
untreated steel panels were electrocoated in the paint, cured and
evaluated generally in accordance with General Motors Scab Corrosion
testing method TM54-26.
For the purpose of comparison, identical substrates were electrocoated and
cured with UNI-PRIME cationic electrodeposition paint available from PPG
Industries, Inc. and compared with the substrates coated in accordance
with the invention. The UNI-PRIME paint, specifically ED 3150, contained
lead.
To 1150.3 grams of the dispersion of Example 3 was added 80.6 grams of a
36.7 percent solids dispersion of the JEFFAMINE D-2000 flexibilizing
adduct described in Example 2, 22.6 grams of the formal of
2-(2-n-butoxyethoxy) ethanol, 13.3 grams of 2-hexoxyethanol, 286.7 grams
of a pigment paste which contributed 11.6 grams of dibutyltin oxide, 3.4
grams of carbon black and 124.4 grams of titanium dioxide (but no lead)
and a total of 1446.5 grams of deionized water. Initially this paint had a
pH of 5.56 and a conductivity of 1269 micromhos. A 20 percent
ultrafiltration and replenishment with deionized water changed this to
5.65 and 1150, respectively.
Test panels were electrocoated at 215 volts for 2 minutes at an 85.degree.
F. bath temperature. After rinsing with deionized water and air-drying,
the panels were baked for 30 minutes at 340.degree. F. and then subjected
to GM Scab Corrosion cyclic testing versus PPG ED 3150 electrodeposition
paint, which contains lead.
After 20 cycles over zinc phosphate pretreated-chromic acid rinsed steel,
this test paint was rated 6 versus 6 for ED 3150. Over untreated steel,
the ratings were 1 versus 3, respectively.
COMPARATIVE EXAMPLE 5
This Example shows the preparation of a cationic water-dispersible resin
similar to Examples 1 and 3 but using the blocked isocyanate crosslinker
of Example C. The dispersion was then used to formulate a lead-free
cationic electrodeposition paint which was electrodeposited over zinc
phosphate pretreated, chromic acid rinsed steel panels and untreated
non-phosphated electrogalvanized steel panels and untreated steel panels.
The cured coated panels were then evaluated for scab corrosion resistance.
The cationic water dispersible resin was prepared as follows: A 3-liter
flask equipped with a stirrer, a condenser, a nitrogen inlet and a
thermometer was charged with 1021.3 grams of the crosslinker solution of
Example C, 798.8 grams (4.27 equivalents) of bisphenol A diglycidyl ether,
153.9 grams (2.80 equivalents) of resorcinol and 186.6 grams of MIBK.
Under a nitrogen blanket and with stirring, this mixture was heated to
90.degree. C. At 90.degree. C., 1.9 grams of benzyl dimethylamine was
added and the temperature was raised to 105.degree. C. After one hour at
105.degree. C., an additional 2.5 grams of benzyl dimethylamine was added
and 105.degree. C. was held until an epoxy equivalent of 1444 was reached,
evidencing a viscosity of Q+ at 60 percent solids in 1-methoxy-2-propanol.
At that point, 40.3 grams (0.11 equivalents) of diethylene triamine
diketimine solution, 27.3 grams (0.21 equivalents) of
N-(2-hydroxyethyl)-piperazine, 52.6 grams (0.14 equivalents) of
dicocoamine, 40.8 grams (0.54 equivalents) of N-methylethanolamine and 9.7
grams (0.06 equivalents) of o-t-butylphenol were added. The temperature
was adjusted to 115.degree. C. and held there for one hour. The viscosity
of the resin was determined to be V-W at 60 percent solids. Of this resin,
2000 grams was then dispersed in a solution of 42.1 grams (0.43
equivalents) of sulfamic acid and 28.4 grams of the surfactant mixture of
Example 1 in 704.9 grams of deionized water. After one hour a total of
3376.1 grams of deionized water was gradually added accompanied by
thorough mixing. The resulting dispersion was warmed to
61.degree.-63.degree. C. and a vacuum was applied to remove water and
volatile organic solvents, yeilding a stripped product at 37.3 percent
solids.
A lead-free cationic electrodeposition paint was prepared using the aqueous
cationic resinous dispersion prepared as described above. Zinc
phosphate-chromic acid rinse pretreated steel panels, untreated
non-phosphated electrogalvanized steel panels and untreated steel panels
were electrocoated in the paint, cured and evaluated generally in
accordance with General Motors Scab Corrosion testing method TM54-26. For
the purposes of comparison, identical substrates were electrocoated and
cured with UNI-PRIME cationic electrodeposition paint (ED 3150) available
from PPG Industries, Inc. and with the cationic electrodeposition paint
containing an acid functional blocked isocyanate crosslinker as described
in Example 1.
To 1166.3 grams of the dispersion was added 78.8 grams of a 37.6 percent
solids dispersion of a JEFFAMINE D-2000 flexibilizing adduct described in
Example 2, 29.6 grams of PARAPLEX WP-1 (product of Rohm and Haas), a total
of 23.9 grams of 2-hexoxyethanol and 279.4 grams of a pigment paste which
contributed 11.6 grams of dibutyltin oxide, 3.4 grams of carbon black and
124.4 grams of titanium dioxide (but no lead). Finally, 1453.0 grams of
deionized water was added to yield a paint with pH of 5.89 and
conductivity of 1434 micromhos. A 20 percent ultrafiltration and
replenishment with deionized water changed this to 5.71 and 1171,
respectively.
Test panels were electrocoated at 300 volts for 2 minutes at a bath
temperature of 95.degree. C. to give about 1.16 mil film build. After
rinsing with deionized water and air drying, the panels were baked for 30
minutes at 340.degree. F. and then subjected to GM Scab Corrosion cyclic
testing versus PPG ED 3150 electrodeposition paint containing lead as well
as a paint made with the cationic water-dispersible resin of Example 1 and
formulated in a manner similar to this example and electrodeposited at 240
volts for 2 minutes at 85.degree. F. to give about 1.18 mil film build.
The relative ratings after 20 cycles of testing were as follows:
__________________________________________________________________________
Test Results Over Steel Substrates
Untreated
Zinc Phosphate
Non-Phosphated
Pretreated-Chromic
Electro-
Paint Example
Acid Rinse
galvanized
Untreated
__________________________________________________________________________
Comparative Example 5
8 5 1
UNI-PRIME 7 5 5
Paint Containing Acid
7 5 4
Functional Blocked
Isocyanate Crosslinker
__________________________________________________________________________
The data summarized immediately above shows that the paint containing acid
functional blocked isocyanate crosslinker provides better corrosion
resistance over untreated steel substrates compared to a similar paint
containing a blocked isocyanate crosslinker which does not have acid
functionality (Comparative Example 5). The paint containing the acid
functional blocked isocyanate crosslinker provides almost as good
corrosion resistance over untreated steel substrates as does the lead
containing paint (UNI-PRIME).
COMPARATIVE EXAMPLE 6
This Example shows the preparation of a cationic water-dispersible resin
similar to Examples 1 and 3 but using the blocked isocyanate crosslinker
of Example D. In this example, the partially blocked isocyanate
crosslinker is incorporated into the resin backbone by reaction of the
isocyanate groups with hydroxyl groups. The dispersion was then used to
formulate a lead-free cationic electrodeposition paint which was
electrodeposited over untreated steel panels and untreated non-phosphated
electrogalvanized steel panels. The cured, coated panels were then
evaluated for scab corrosion resistance.
The cationic water-dispersible resin was prepared as follows: A 5-liter
flask equipped with a stirrer, a condenser, a nitrogen inlet and a
thermometer was charged with 748.2 grams (4.00 equivalents) of bisphenol A
diglycidyl ether, 252.1 grams (1.04 equivalents) of a 1:7 bisphenol
A-ethylene oxide diol, 144.4 grams (2.63 equivalents) of resorcinol and
49.9 grams of methyl isobutyl ketone. While stirring under a nitrogen
blanket, the mixture was heated to 90.degree. C. and held there until all
of the resorcinol dissolved. At that point, 849.6 grams (0.83 equivalents)
of the partially blocked polyisocyanate of Example D and 49.9 grams of
methyl isobutyl ketone were added. The temperature was adjusted to
90.degree. C. and held there until the 4.4 micron peak in the infrared
spectrum was negligible. Then 1.6 grams of benzyl dimethylamine was added
and the temperature was raised to 105.degree. C. and held there for one
hour, whereupon an additional 2.3 grams of benzyl dimethylamine was added.
The temperature was maintained at 105.degree. C. until an epoxy equivalent
of 1480 on solids was reached (evidencing a V+ Gardner-Holdt viscosity at
60 percent solids in 1-methoxy-2-propanol), that occurrence coinciding
with the prompt, sequential addition of 36.3 grams (0.29 equivalents) of
diethylene triamine methyl isobutyl ketone diketimine at about 72 percent
in methyl isobutyl ketone, 25.3 grams (0.19 equivalents) of
N-(2-hydroxyethyl)-piperazine, 48.7 grams (0.13 equivalents) of
dicocoamine, 37.8 grams (0.50 equivalents) of N-methylethanolamine and 9.0
grams (0.06 equivalents) of o-t-butylphenol. The temperature was adjusted
to 115.degree. C., and held there for one hour. Under reduced pressure, 85
grams of volatiles was removed and 1775 grams of this resin was dispersed
by pouring into a stirred solution of 593.2 grams of deionized water, 37.7
grams (0.39 equivalents) of sulfamic acid and 24.9 grams of the surfactant
mixture used in the above examples. After stirring the heavy dispersion
for one hour, a total of 3541.4 grams of deionized water was gradually
added in small portions with good blending and then the whole was heated
to 60.degree.-62.degree. C., whereupon a vacuum was applied and sufficient
volatiles were removed to ultimately yield a 32.2 percent solids
dispersion.
To 1740.0 grams of this dispersion was added 93.8 grams of a 40.7 percent
solids dispersion of a JEFFAMINE D-2000 flexibilizing adduct, 29.1 grams
of the formal of 2-(2-n-butoxyethoxy)ethanol, 82.5 grams of a 15.4 percent
solids dispersion of a microgel flow control additive, 16.8 grams of
2-hexoxyethanol, and 306.8 grams of a pigment paste which contributed 4.0
grams of carbon black, 144.3 grams of titanium dioxide, 13.5 grams of
dibutyltin oxide (but no lead) to this mixture. Finally, 1531.0 grams of
deionized water was added to yield a paint which, after ultrafiltrative
removal of 20 percent of the total paint weight and replenishment with
deionized water, had a conductivity of 995 micromhos and a pH of 5.56.
Panels were electrocoated at 275 volts for 2 minutes at a bath temperature
of 87.degree. F. After rinsing with deionized water and air drying, the
panels were baked at 340.degree. F. for 30 minutes and subjected to
General Motors Scab Corrosion testing method TM54-26. For the purpose of
comparison, identical substrates were electrocoated and cured with
UNI-PRIME cationic electrodeposition paint (ED 3150) available from PPG
Industries, Inc.
Over GM bare steel coach joints, lead-free paint rated 4 while ED 3150
rated 9. Over untreated steel panels, the lead-free paint rated 1 versus 4
for ED 3150, while over untreated non-phosphated electrogalvanized steel
panels, the lead-free paint rated 1 versus 4 for ED 3150, all after 20
cycles.
Top